Green trisazo dyestuffs and a process for their manufacture



' trisazo dyestufi's suitable for dyeing-leather in to a process for their Patented May' 28, I940- PATENT? 'forslcs GREEN ,TRISAZO DYESTUFFS AND A race ss FOR THEIR MANUFACTURE Heinrich Lier, Basel, Switzerland, assignor to the firm Chemical Works, formerly Sandoz, Basel,

Switzerland- .No: Drawing. Application February 24, 1939, Se-

rial No. 3 1

The present'invention relates to new'green fast green shades and manufacture.

Applicant has found that new valuable green trisazo dyestuffs may be, obtained by coupling in an acid medium a diazo compound deriving frorn'ianamine of the benzene and naphthalene series with a sulphonated 1,8,-aminonaphthol and combining the monoazo dyestufi thus obtained with a tetrazo compound deriving from benzene, naphthalene ordiphenyl series in such a manner, that one of the diazo groups becomes combined with the monoazo dyestui'f, the other 'diazo group being coupled-with an acyl acetic acid arylide. The dyestuffs obtained in this manner are built up as it is shown by the followinggeneral formula wherein A stands for a dia'zo compound deriving from: an amine of the benzene and naphthalene series, B stands for a bivalent radical of the benzene, naphthalene and diphenyl series, C'

tives containing halogen, nitro c'arboxy, alkoxy aryloxy, amino-, -a-1kylamino, acylamino, sulioylamino. or sulphamido groups. Such suitable components are for instance the I di-azo:.com-

pounds of the ortho-, metaand para-aminobenzenesulphonic acids, aniline-2.5-disu1phonic acid, p-toluidine-o-sulphonic acid, p-chloraniline-o-sulphonic acid, 'p-nitraniline-sulphonic acids,- p-amidoacetanilide-o-sulphonic acid, naphthionic acid, amino-R-acicl and similar compounds, V

Astetrazo compound B the applicant uses tetrazotized diamines like tetrazotized, benzidine,

benzidine-sulphone, tetrazotized halogenated benzidines, monoor disulphonic acids of the .benzidines and similar compounds.

For the preparation of the new trisazo-dyestuffs there can be used instead of the tetrazo compounds also monodiazotized, diamines or diazotized nitranilineslikemetaor paranitransimilar compounds.

258,330; In Switzerland. 'March 5,

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iline and their sulphonic acids, or the respective acylaminoarylarnines like acylaminoaniline, whereby the nitrorespectively the acylamino groups contained in these compounds are after coupling reduced to the amine group or saponi- 'fied, whereby aminoazo dyestuffs will be obtained, which may [be further diazotized and couplediwith the acylacetie acid arylides. H As aminonaphtholsulphonic acid applicant. preferably uses 1.8- aminonaphthol 3.6 disulphonic acid,- l.8-aniinonaphthol-afi-disulphonic acid, 1B-aminonaphtholi-sulphonic acid and similar sulphonated compounds.

As end component C applicant uses acylacetic acid aryl'ides; especially the arylides of the aceto acetic. acid such as acetoacetic acid anilide, -p-to1- uidide, -m-xylidide, o-chloranilide, -2;5 dichloranilide, -o-anisidide, -p-anisid ide, -p-cresiclide,

-a-naphthylamide, ciliacetoacetylbenzidine and The new green dyestuffs obtained as herein above described possess various constitution. and solubility according to'theselection of the com-- ponents used for theirmanufacture.

In the drystate they are darkpowders easily soluble in. water with a. yellowishgreen to a greenish blue coloration. They dye leather of different; tanning in fast green level and brilliant shades. As compared to the known dyestuffs" which contain instead of the acylacetic acidarylidea as end componenta phenol or a phenolcar boxylie acid, they possess a much. better fastness to lig-ht anda better stabilitytowards the action of acidsand. alkalies. The new dyestuffs possess iiurthenthe property of dyeing leather which has t been tanned. with mineral: or vegetable tanning agents in very level shades with a good penetration of the color and the dyeingvbaths are easily exhausted -on addition. of small quantities of acid] They canfbe used'for. through-dyeing. or

brush dyeing, or dyeing by, the spraying method of. various sorts of leather and possess, when app1i'ed. by these methods, valuable penetrating properties.

one object of' the present invention is the process for the manufacture of green'trisazo dyestuffs suitable. for dyeing leather comprising diphenyline, o-tolidine, m tolidine, .dianisidine, 1 the Steps first emprmg in an acid medium diazo compound. deriving froman amine of the benzene and naphthalene series with a suI phomated 1.8-aminonaphthol combining the monoazo: dyestufi thus obtained with anequimolecu-lar a dyestuff thus obtained with an acylacetic acid arylide. 7

Another object of the present invention are the new green trisazo dyestuffs, eminently suitable for dyeing leather, which respond to the general formula IIIHR OH X SQsH wherein A stands for a radical deriving from a diazo compound deriving from an amine of the benzene and napthalene series, B stands for a bivalent radical of the benzene, naphthalene and diphenyl series, C stands for an acylacetic acid arylide and X represents hydrogen and a sulphonic acid group.

Example 1 1 mol. of diazotized an1inobenzene-z.o-disul phonic acid is coupled in weak mineral acid with 1 mol. of 1.8 aminonaphthol-3.6-disulphonic acid. By careful addition of some acid binding agent such as sodium bicarbonate, the complete coupling is rapidly reached. The weal: mineral acid solution is then carefully made alkaline with sodium carbonate and a solution of 1 mol. tetrazo benzidine is slowly added thereto. When the tetrazo-benzidine has completely disappeared, an alkaline solution of 1 mol. acetoacetic acid anilide is added thereto, whereby the final coupling takes place very rapidly and the solution becomes colored intensively green.

The solution is then stirred during several hours, heated up to 60 (3., carefully acidulated and the dyestuff carefully salted out. After filtration and drying the dyestuii is obtained in the form of a dark powder, which is easily soluble in water with an emerald green coloration. This dyestuif dyes leather which has been tanned with mineral or vegetable tanning agents in beautiful deep green shades, which possess a more brilliant shade as compared to theshade obtained with dyestuffs possessing phenols as end component;

The new dyestufi dyes for instance chrome suede leather in beautiful, level green shades, which are not cleared up on subsequent fluffing, due to the good penetration of the dyestufi.

The new dyestufi can also be used in a cold acidulated solution for brush-dyeing and spraydyeing of leather, without givinga bronze-effect.

By using instead of the aminobenzene-2.5- disulphonic acid compounds such as sulphanilic acid or metanilic acid or aniline-o-sulphonic acid or p-toluidine-o-sulphonic acid, dyestuffs will be obtained which possess a similar shade, but a somewhat decreased solubility.

is given on penetration, but where it is very important to obtain a level superficial dyeing of the leather.

A similar dyestuff will also be obtained when instead of tetrazobenzidine, tetrazodianisidine is used.

More difiicultly soluble and somewhat bluer dyestuffs will be obtained by using as end component acetoacetic acid-ochloranilide, -2.5 -dichloranilide, -anaphthylamide and similar compounds.

Ewample 2 1 mol. of diazotized sulphanilic acid is coupled Such dyestuifs 1 are especially used in the cases, where less value in weak mineral acid solution with 1 mol. of 1.8- aminonaphthol-3.6-disulphonic acid and the monoazo dyestuff thus obtained combined with tetrazobenzidine and acetoacetic acid anilide in the manner described in Example 1.

The green dyestufi thus obtained dyes box leather in fast and level green shades.

Example 3 The disazodiazo dyestuif obtained as intermediate product in the manner described in Example 1 by combining 1 mol. of aniline-2.5-disulphonic acid with 1 mol. of 1.8-aminonaphthol-3.6-disulphonic acid and 1 mol. of tetrazobenzidine is cou- .pled in alkaline medium with 1 mol. of acetoacetic acid-o-anisidide. The dyestufi' thus obtained dyes leather in clearer green shades than the respective dyestuif containing as end component the acetoacetic acid anilide.

What I claim is:

1. The new green trisazo dyestuffs of the general formula wherein A stands for a sulphonated radical deriving from a diazo compound deriving from an amine of the benzene and naphthalene series and X stands for one member of the group consisting of hydrogen and a sulphonic group, which dyestuifs are in the dry state dark powders, easily soluble in water with a yellowish green to greenish blue coloration and which dye vegetable and mineral tanned leather in fast green shades.

2. The new green trisazo dyestuffs of the general formula wherein A stands for a radical deriving from a diazo compound deriving from an amine of the benzene and naphthalene series, which dyestufi's are in dry state dark powders, easily soluble in water with a yellowish green to greenish blue coloration and which dye vegetable and mineral tanned leather in fast green shades.

4. The new green dyestufi of the foimula:

5. The new green dyestuff of the formula; I

6. The new green dyes tlifif pf the fqrmula:

SOaH 

